Electron Spin, Spectra and Many Electron Atoms: Pilani

BITS Pilani Campus Pilani
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General Chemistry Lecture 7:
Electron Spin, spectra and many electron atoms

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Radial wavefunction
The general form of the radial part of the hydrogenic atom wavefunctions, obtained by solving the radial Schrodinger equation, and applying the necessary conditions on the solutions, may be written Rnl(r) r l. (Polynomial of degree n-l-1). e-Zr/na0 The first factor determines the behaviour at r = 0 (only l = 0 wavefunctions are nonzero at the origin) Click to edit Master subtitle style The second factor determines the number of nodes (nl-1) The third ensures that the function goes to 0 as r
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BITSPilani, Pilani Campus
Radial wavefunction
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s orbitals
Spherically symmetric, angular part is just a constant States of zero orbital angular momentum
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s orbitals
Spherically symmetric, angular part is just a constant States of zero orbital angular momentum
1s
2s 3s
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p orbitals angular parts
cos (pz) sin sin (p ) y l = 1, ml = 0 1 nodal surface (xy)

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sin cos (px) l = 1, ml = 1 or 1 1 nodal surface (yz)

l = 1, ml = 1 or 1 1 nodal surface (xz)
P orbitals boundary surfaces
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p orbitals density of dots
2pz
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3pz
d orbitals angular parts
2 nodal planes
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Electron spin
Intrinsic angular momentum, and associated magnetic moment, characteristic of electron, a property like its mass, charge etc. First indicated by spectroscopic features, eg., the doublet Na D line Confirmed by the Stern Gerlach experiment. Click atoms passed through a magnetic A beam ofto edit Master subtitle style field strongly inhomogeneous in, say, the z direction. Two beams emerge the magnetic moment can take only two orientations with respect to the chosen axis.
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Stern Gerlach experiment

Classically expected result
z-axis Ag atoms Experimental Result

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Electron spin
Electron described by intrinsic spin angular momentum quantum number s= ie., angular momentum of magnitude [1/2(1/2 + 1)]1/2 = (3/2) The component of electron spin along any axis in space, say to edit Master subtitle styleon one of two values the z axis, can take Click /2 or -/2, denoted by the quantum number ms = 1/2 ( state) or 1/2 ( state)
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Spin states of electron
The state of the electron in the hydrogenic atom is therefore fully specified by the four quantum numbers n, l, ml, and ms. Spin orbital = Spatial orbital x spin function eg., 1s
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Spin
All fundamental particles have characteristic spin values. Protons and Neutrons are also spin particles like electrons. Photons are spin 1 particles. All particles may be classified as BOSONS Click to edit (spin quantumMaster subtitle style or a positive number is zero integer, ie., s = 0,1,2,), or FERMIONS (spin quantum number is a positive half-integer, ie., s = 1/2, 3/2,.. )
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Spectral Transitions
In the one electron atom, spectral line occurs when electron makes a transition between shells with principal quantum numbers ni and nf. However, not all transitions between all available orbitals are possible, For example, while 2p to 1s, and 3p to 1s are Click to edit Master subtitle style allowed transitions, 2s to 1s or 3d to 1s are forbidden transitions. A statement about which spectroscopic transitions are allowed is called a selection rule
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Grotrian Diagram
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Selection rule one electron atom

For the one electron atom, the selection rule is just the statement of the conservation of angular momentum, keeping in mind that a photon carries (spin) angular momentum of magnitude corresponding to spin quantum number s = 1. Click to edit Master subtitle style Selection rule: l = 1 ml = 0, 1
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Many electron atoms

The Schrodinger equation cannot be solved exactly for atoms with two or more electrons. However, refined approximations allow one to compute wavefunctions and energies quite accurately. Orbital approximation: Approximate the wavefunction as a product of one electron functions or orbitals. (How correspondingly are Click to edit Master subtitle style we approximating the Hamiltonian?) (1,2,) = 1(1)2(2).. Each orbital may be thought of as being hydrogen-like with an effective nuclear charge
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Orbital approximation He atom

The orbital approximation allows us to express the electronic structure of an atom in terms of its configuration, the list of occupied orbitals. For example, if one disregards the inter-e;ectronic repulsion, the ground state wavefunction of He may be written as (1,2) = (8/a03)1/2exp(-2r1/a0) (8/a03)1/2 exp(-2r2/a0) corresponding to the configuration 1s2, with the 1s orbital being somewhat more compact style in H. Click to edit Master subtitle than What about Li? (Can all 3 electrons occupy 1s orbital ?)
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Pauli exclusion principle

No more than two electrons may occupy a given orbital, and if two electrons do occupy one orbital, then their spins must be paired. (More later). The two electrons with paired spins () have zero net spin angular momentum. This principle forms the basis of the electronic structure of atoms, chemical periodicity, and molecular Click to edit Master subtitle style structure. The third electron in Li must enter the n = 2 shell, but the 2s or the 2p?
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Shielding and penetration

Shielding: In a many electron atom, each electron is shielded from the nucleus by the others, and to a first approximation, each electron may be thought of as experiencing an effective nuclear charge. Click to edit Master subtitle style The effective nuclear charge experienced by an electron will be determined by its probability density distribution, and this in turn by its wavefunction
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Penetration
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Order of occupation
The greater penetration of an s electron compared to a p electron of the same shell implies that it experiences a greater effective nuclear charge. In turn, the effective nuclear charge experienced by the p electron will be greater than that for a d electron in the same shell. In general therefore, in the same shell of a manyClick to edit Master subtitle energies of the orbitals electron atom, the order of style is s < p < d < f. The ground electronic configuration of Li is therefore 1s22s1, or [He]2s1
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Aufbau principle, Hunds rule

Order of occupation of atomic orbitals. Rules: 1. 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 5d 4f 6p 2. Each orbital may accommodate up to two electrons. 3. Electrons occupy different orbitals of a given subshell edit Masterdoubly occupying any one of before subtitle style Click to them. 4. In its ground state, atom adopts configuration with greatest number of unpaired electrons (Hunds rule)
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Hunds rule, periodicity

Eg., C 1s22s22px12py1 N 1s22s22px12py12pz1 Origin of Hunds rule: Spin Correlation Electrons in different orbitals with parallel spins have a quantum mechanical tendency to stay apart. This allows slight shrinkage, leading to greater attraction to nucleus.
Periodicity: Neon with ten electrons has the configuration [He]2s22p6, which completes the L shell. Na has configuration [Ne]3s1, with properties like Li
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Periodic Table
Ar - [Ne]3s23p6 effectively like closed shell. Next the 4s orbitals are filled (penetration). K [Ar]4s1 (like Na) and Ca [Ar]4s2 (like Mg). The 3d orbitals are filled next from Sc to Zn the first transition series, d-block elements Sc [Ar]3d14s2, Zn [Ar]3d104s2 (Y to Cd, and edit to Hg are second & third series). Click to La Master subtitle style Beyond this from Ga to Kr, the 4p orbitals are filled (the first long period) In periods 6 and 7 also have f-block elements
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Electron Spin, Spectra and Many Electron Atoms: Pilani

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General Chemistry Lecture 7: